Covalent functionalization of carbon nanotubes grown on a surface

Abstract

The present invention is related to a new method for directly covalently functionalizing carbon nanotubes (CNTs) grown on or attached to a surface. The invention also features devices that are comprised of CNTs.

What is claimed is: 
     
         1 . A method of functionalizing a carbon nanotube (CNT) on a surface of a chip according to formula I:
   (SURFACE-CNT-A-L-(FG) n ),   wherein (A) is the attachment to the CNT, (L) is a linker between the attachment on the CNT and one or more functional group (FG)n.   
     
     
         2 . The method of  claim 1 , further comprising:
 a cycloaddition step;   an amide coupling step; and   a CuAAC step.   
     
     
         3 . The method of  claim 1 , wherein the functional group is covalently attached. 
     
     
         4 . The method of  claim 1 , wherein the surface conducts electricity, heat or light. 
     
     
         5 . The method of  claim 1 , wherein the surface is an insulator of electricity, heat or light. 
     
     
         6 . The method of  claim 1 , wherein the surface is not electric. 
     
     
         7 . The method of  claim 1 , wherein the surface is a metal film. 
     
     
         8 . A method of covalently functionalizing carbon nanotubes (CNTs) grown on a surface of formula I (SURFACE-CNT-A-L-(FG)n), comprising
 a cycloaddition step;   an amide coupling step; and   a CuAAC step,   wherein (A) is the attachment to the CNTs, (L) is a linker between the attachment on the CNTs and the functional groups (FGs).   
     
     
         9 . The method of  claim 1  or  8  wherein (A) is a pyrrolidine ring substituted with L on either the nitrogen atom or on C2 or C5 of the pyrrolidine ring system. 
     
     
         10 . The method of  claim 1  or  8 , wherein, (A) is substituted with R1 and R2. 
     
     
         11 . The method of  claim 9 , wherein the C3 and C4 in (A) originate from the CNT structure. 
     
     
         12 . The method of  claim 1  or  8 , wherein R1 and R2 are each and independently selected from hydrogen, (C 1 -C 15 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heterocyclyl, or any of these groups (except hydrogen) optionally substituted with one or more halogen (F, Cl, Br or I) atoms and/or one or more of the following groups, OH, CN, NO 2 , (C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxyC(O), halogen substituted (C 1 -C 12 )alkyl, (C 3 -C 6 )cycloalkyl, aryl, heterocyclyl, optionally interrupted by one or more, O, N, S, P, Si or B atoms. 
     
     
         13 . The method of  claim 1  or  8 , wherein L is a linker between the attachment (A) on the CNTs and the FG(s), selected from the group consisting of: (C 1 -C 30 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heterocyclyl, and any of these groups (except hydrogen) optionally interrupted by one or more O, N, S, P, Si, or B atoms, and/or one or more carbonyls, and/or substituted by one or more halogen (F, Cl, Br or I) atoms and/or one or more of the following groups, (C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxyC(O), halogen substituted (C 1 -C 12 )alkyl, (C 3 -C 6 )cycloalkyl, aryl, heterocyclyl, optionally interrupted by one or more, O, N, S, P, Si or B atoms. 
     
     
         14 . The method of  claim 13 , wherein one or more of the carbon atoms in (L) is substituted by one (FG). 
     
     
         15 . The method of  claim 13 , wherein the (L) is bound to the nitrogen or C2 or C5 on the pyrrolidine ring system. 
     
     
         16 . The method of  claim 2  or  8 , wherein the cycloaddition reaction is a 1,3-dipolar cycloaddition. 
     
     
         17 . The method of  claim 1  or  8 , wherein the (FG) is selected from the group consisting of: amine, azide, alkyne, carboxylic acid, an activated ester of a carboxylic acid, thiol, acid chloride, acid fluoride, sulfonyl chloride, isocyanate, isothiocyanate, aryl halide (F, Cl, Br or I), alkyl halide (F, Cl, Br or I), maleimide, ketone, aldehyde, alcohol, alkene, triflate, nitro, nitrile, boronic acid, boronic ester and a trifluoroborate salt. 
     
     
         18 . The method according to  claim 1  or  8 , wherein the method is performed in a solvent selected from the group consisting of: toluene, benzene, chlorobenzene, dichlorobenzene, poly halogenated benzene derivatives, trifluoro methylbenzene, CH 2 Cl 2 , CHCl 3 , CCl 4 , DCE, DMF, DMA, NMP, dioxane, THF, 2-MeTHF and DMSO. 
     
     
         19 . The method of  claim 1  or  8 , wherein the method is carried out at a temperature from 20-250° C. 
     
     
         20 . The method of  claim 1  or  8 , wherein the reaction time is between 1-48 hours. 
     
     
         21 . A composition comprising a carbon nanotube (CNT) on a surface of a chip according to formula I:
   (SURFACE-CNT-A-L-(FG) n ),   wherein (A) is the attachment to the CNT, (L) is a linker between the attachment on the CNT and one or more functional group (FG)n.   
     
     
         22 . The composition of  claim 21 , wherein the functional group is covalently attached. 
     
     
         23 . The composition of  claim 21 , wherein the surface conducts electricity, heat or light. 
     
     
         24 . The composition of  claim 21 , wherein the surface is an insulator of electricity, heat or light. 
     
     
         25 . The composition of  claim 21 , wherein the surface is not electric. 
     
     
         26 . The composition of  claim 21 , wherein the surface is a metal film. 
     
     
         27 . The composition of  claim 21 , wherein (A) is a pyrrolidine ring substituted with L on either the nitrogen atom or on C2 or C5 of the pyrrolidine ring system. 
     
     
         28 . The composition of  claim 21 , wherein, (A) is substituted with R1 and R2. 
     
     
         29 . The composition of  claim 27 , wherein the C3 and C4 in (A) originate from the CNT structure. 
     
     
         30 . The composition of  claim 21 , wherein R1 and R2 are each and independently selected from hydrogen, (C 1 -C 15 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heterocyclyl, or any of these groups (except hydrogen) optionally substituted with one or more halogen (F, Cl, Br or I) atoms and/or one or more of the following groups, OH, CN, NO 2 , (C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxyC(O), halogen substituted (C 1 -C 12 )alkyl, (C 3 -C 6 )cycloalkyl, aryl, heterocyclyl, optionally interrupted by one or more, O, N, S, P, Si or B atoms. 
     
     
         31 . The composition of  claim 21 , wherein L is a linker between the attachment (A) on the CNTs and the FG(s), selected from the group consisting of: (C 1 -C 30 )alkyl, (C 3 -C 8 )cycloalkyl, aryl, heterocyclyl, and any of these groups (except hydrogen) optionally interrupted by one or more O, N, S, P, Si, or B atoms, and/or one or more carbonyls, and/or substituted by one or more halogen (F, Cl, Br or I) atoms and/or one or more of the following groups, (C 1 -C 12 )alkyl, (C 1 -C 12 )alkoxyC(O), halogen substituted (C 1 -C 12 )alkyl, (C 3 -C 6 )cycloalkyl, aryl, heterocyclyl, optionally interrupted by one or more, O, N, S, P, Si or B atoms. 
     
     
         32 . The composition of  claim 31 , wherein one or more of the carbon atoms in (L) is substituted by one (FG). 
     
     
         33 . The composition of  claim 31 , wherein the (L) is bound to the nitrogen or C2 or C5 on the pyrrolidine ring system. 
     
     
         34 . The composition of  claim 21 , wherein the (FG) is selected from the group consisting of: amine, azide, alkyne, carboxylic acid, an activated ester of a carboxylic acid, thiol, acid chloride, acid fluoride, sulfonyl chloride, isocyanate, isothiocyanate, aryl halide (F, Cl, Br or I), alkyl halide (F, Cl, Br or I), maleimide, ketone, aldehyde, alcohol, alkene, triflate, nitro, nitrile, boronic acid, boronic ester and a trifluoroborate salt. 
     
     
         35 . A device comprising a one or a plurality of CNT structures according to  claim 21 . 
     
     
         36 . The device according to  claim 35 , wherein the CNT structures comprise a high surface area 3D set up that can be functionalized in solid, liquid, gaseous or liquid crystal or any other phases. 
     
     
         37 . A device according to  claim 36 , wherein the functionalized CNTs are used as sensors, energy storage devices, photovoltaic devices or imaging devices. 
     
     
         38 . The device according to  claim 35 , wherein there is energy exchange, transfer or storage between the CNT structures and the functionalizations or between the plurality of CNT structures that are functionalized.